Materials for organic electroluminescent devices

ABSTRACT

The present invention relates to mixtures comprising at least one phosphorescent dopant and at least one compound of one of the formulae (1) and (2), and the use thereof in electronic devices, especially in organic electroluminescent devices.

The present invention describes mixtures of quinazolinone derivativesand phosphorescent dopants, and the use of quinazolinone derivatives andtriplet matrix materials in organic electroluminescent devices. Theinvention further relates to a process for preparing the compounds ofthe invention and to electronic devices comprising these compounds.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are used as functional materials is described,for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No. 5,151,629, EP0676461 and WO 98/27136. Emitting materials used are frequentlyorganometallic complexes which exhibit phosphorescence rather thanfluorescence. For quantum-mechanical reasons, up to four times theenergy efficiency and power efficiency is possible using organometalliccompounds as phosphorescent emitters. In general terms, there is still aneed for improvement in OLEDs, especially also in OLEDs which exhibittriplet emission (phosphorescence), for example with regard toefficiency, operating voltage and lifetime.

The properties of phosphorescent OLEDs are not just determined by thetriplet emitters used. More particularly, the other materials used, forexample matrix materials, are also of particular significance here.Improvements to these materials can thus also lead to distinctimprovements in the OLED properties.

According to the prior art, among other materials, indolocarbazolederivatives (for example according to WO 2007/063754 or WO 2008/056746)or indenocarbazole derivatives (for example according to WO 2010/136109or WO 2011/000455), especially those substituted by electron-deficientheteroaromatics such as triazine, are used as matrix materials forphosphorescent emitters. In addition, for example, bisdibenzofuranderivatives (for example according to EP 2301926) are used as matrixmaterials for phosphorescent emitters. However, there is still a needfor improvement in the case of use of these matrix materials, especiallyin relation to the efficiency, the lifetime and the operating voltage ofthe device.

It is an object of the present invention to provide compounds suitablefor use in phosphorescent OLEDs, especially as matrix material. Moreparticularly, it is an object of the present invention to provide matrixmaterials suitable for green- and blue-phosphorescing OLEDs.

It has been found that, surprisingly, a mixture comprising at least onephosphorescent dopant and at least one compound of the followingformulae (1) and (2) has improvements over the prior art, especiallywhen used in organic electroluminescent devices:

-   where the symbols and indices used are as follows-   X is the same or different at each instance and is N or CR³, where    not more than 2X per heteroaryl group are N;-   L is the same or different at each instance and is an (m+n)-valent    aromatic or heteroaromatic ring system which has 5 to 60 aromatic    ring atoms and may be substituted by one or more R⁴ radicals;-   R¹ is the same or different at each instance and is H, D, F, Cl, Br,    I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂, Si(R⁴)₃,    B(OR⁴)₂, OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkoxy group    having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or    thioalkoxy group having 3 to 40 carbon atoms and may be substituted    in each case by one or more R⁴ radicals, where one or more    nonadjacent CH₂ groups may be replaced by C≡C, Si(R⁴)₂, Ge(R⁴)₂,    Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴ and where    one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or    NO₂, or an aromatic or heteroaromatic ring system which has 5 to 60    aromatic ring atoms and may be substituted in each case by one or    more R⁴ radicals, or an aryloxy or heteroaryloxy group which has 5    to 60 aromatic ring atoms and may be substituted by one or more R⁴    radicals, or a combination of these systems; at the same time, two    or more R¹ substituents may also form a mono- or polycyclic,    aliphatic or aromatic ring system with one another;-   R² is the same or different at each instance and is H, D, F, Cl, Br,    I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂, Si(R⁴)₃,    B(OR⁴)₂, OSO₂R⁴, N(Ar)₂, a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic    alkyl, alkoxy or thioalkoxy group having 3 to 60 carbon atoms and    may be substituted in each case by one or more R⁴ radicals, where    one or more nonadjacent CH₂ groups may be replaced by C≡C, Si(R⁴)₂,    Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴    and where one or more hydrogen atoms may be replaced by D, F, Cl,    Br, I, CN or NO₂, or an aromatic or heteroaromatic ring system which    has 5 to 60 aromatic ring atoms and may be substituted in each case    by one or more R⁴ radicals, or an aryloxy or heteroaryloxy group    which has 5 to 60 aromatic ring atoms and may be substituted by one    or more R⁴ radicals, or a combination of these systems; at the same    time, two or more R² substituents may also form a mono- or    polycyclic, aliphatic or aromatic ring system with one another;-   R³ is the same or different at each instance and is H, D, F, Cl, Br,    I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂, Si(R⁴)₃,    B(OR⁴)₂, OSO₂R⁴, N(R⁴)₂, a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic    alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and    may be substituted in each case by one or more R⁴ radicals, where    one or more nonadjacent CH₂ groups may be replaced by C≡C, Si(R⁴)₂,    Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴    and where one or more hydrogen atoms may be replaced by D, F, Cl,    Br, I, CN or NO₂, or an aromatic or heteroaromatic ring system which    has 5 to 60 aromatic ring atoms and may be substituted in each case    by one or more R⁴ radicals, or an aryloxy or heteroaryloxy group    which has 5 to 60 aromatic ring atoms and may be substituted by one    or more R⁴ radicals, or a combination of these systems; at the same    time, two or more adjacent R³ substituents may also form a mono- or    polycyclic, aliphatic or aromatic ring system with one another;-   Ar is the same or different at each instance and is an aromatic or    heteroaromatic ring system which has 6 to 60 aromatic ring atoms and    may also be substituted in each case by one or more R⁴ radicals,-   R⁴ is the same or different at each instance and is H, D, F, Cl, Br,    I, CHO, C(═O)R⁵, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, CN, NO₂, Si(R⁵)₃,    B(OR⁵)₂, OSO₂R⁵, N(R⁵)₂, a straight-chain alkyl, alkoxy or    thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic    alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each    of which may be substituted by one or more R⁵ radicals, where one or    more nonadjacent CH₂ groups may be replaced by C≡C, Si(R⁵)₂,    Ge(R⁵)₂, Sn(R⁵)₂, C═O, C═S, C═Se, P(═O)(R⁵), SO, SO₂, O, S or CONR⁵    and where one or more hydrogen atoms may be replaced by D, F, Cl,    Br, I, CN or NO₂, or an aromatic or heteroaromatic ring system which    has 5 to 60 aromatic ring atoms, each of which may be substituted by    one or more R⁵ radicals, or an aryloxy or heteroaryloxy group which    has 5 to 60 aromatic ring atoms and may be substituted by one or    more R⁵ radicals, or a combination of these systems; at the same    time, two or more adjacent R⁴ substituents may also form a mono- or    polycyclic, aliphatic or aromatic ring system with one another;-   R⁵ is the same or different at each instance and is H, D, F, Cl, Br,    I, N(R⁶)₂, C(═O)R⁶, P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶, CR⁶═C(R⁶)₂, CN,    NO₂, Si(R⁶)₃, B(OR⁶)₂, OSO₂R⁶, N(R⁶)₂, a straight-chain alkyl,    alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched    or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon    atoms, each of which may be substituted by one or more R⁶ radicals,    where one or more nonadjacent CH₂ groups may be replaced by R⁶C═CR⁶,    C≡C, Si(R⁶)₂, C═O, C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, S or CONR⁶ and    where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I,    CN or NO₂, or an aromatic or heteroaromatic ring system which has 5    to 60 aromatic ring atoms, each of which may be substituted by one    or more R⁶ radicals, or an aryloxy or heteroaryloxy group which has    5 to 60 aromatic ring atoms and may be substituted by one or more R⁶    radicals, or an aralkyl or heteroaralkyl group which has 5 to 60    aromatic ring atoms and may be substituted by one or more R⁶    radicals, or a combination of these systems; at the same time, two    or more adjacent R⁵ substituents together may also form a mono- or    polycyclic, aliphatic or aromatic ring system;-   R⁶ is the same or different at each instance and is H, D, F or an    aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl    or heteroaryl group which has 5 to 60 ring atoms and may be    substituted by one or more R⁷ radicals, or a combination of these    groups;-   R⁷ is the same or different at each instance and is H, D, F or an    aliphatic hydrocarbyl radical having 1 to 20 carbon atoms;-   m, n are the same or different at each instance and are 0, 1, 2, 3,    4, 5, 6 or 7;-   where-   m+n is equal to or superior to 2.

The bicyclic system in formula (1) is also referred to as thequinazolinone base skeleton to which R¹, R² or R³ bind.

In this context, (m+n)-valent aromatic or heteroaromatic ring systemmeans that m+n quinazolinone radicals are bonded to the aromatic orheteroaromatic ring system. The rest of the unoccupied positions may besubstituted by R⁴.

An aryl group in the context of this invention contains 6 to 60 carbonatoms; a heteroaryl group in the context of this invention contains 2 to60 carbon atoms and at least one heteroatom, with the proviso that thesum total of carbon atoms and heteroatoms is at least 5. The heteroatomsare preferably selected from N, O and/or S. An aryl group or heteroarylgroup is understood here to mean a simple aromatic cycle, i.e. benzene,or a simple heteroaromatic cycle, for example thiophene, etc., or acondensed (fused) aryl or heteroaryl group, for example naphthalene,anthracene, phenanthrene, dibenzofuran, etc. Aromatic systems joined toone another by a single bond, for example biphenyl, by contrast, are notreferred to as an aryl or heteroaryl group but as an aromatic ringsystem.

An aromatic ring system in the context of this invention contains 6 to80 carbon atoms in the ring system. A heteroaromatic ring system in thecontext of this invention contains 2 to 60 carbon atoms and at least oneheteroatom in the ring system, with the proviso that the sum total ofcarbon atoms and heteroatoms is at least 5. The heteroatoms arepreferably selected from N, O and/or S. An aromatic or heteroaromaticring system in the context of this invention is understood to mean asystem which does not necessarily contain only aryl or heteroarylgroups, but in which it is also possible for two or more aryl orheteroaryl groups to be joined by a nonaromatic unit (preferably lessthan 10% of the atoms other than H), for example a carbon, nitrogen oroxygen atom. For example, systems such as fluorene,9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers,stilbene, etc. shall also be regarded as aromatic ring systems in thecontext of this invention, and likewise systems in which two or morearyl groups are joined, for example, by a short alkyl group. Inaddition, aromatic systems joined to one another by a single bond, forexample biphenyl, are referred to as aromatic ring system in the contextof this application.

An electron-deficient heteroaryl group in the context of the presentinvention is defined as a 5-membered heteroaryl group having at leasttwo heteroatoms, for example imidazole, oxazole, oxadiazole, etc., or asa 6-membered heteroaryl group having at least one heteroatom, forexample pyridine, pyrimidine, pyrazine, triazine, etc. It is alsopossible for further 6-membered aryl or 6-membered heteroaryl groups tobe fused onto these groups, as, for example, in benzimidazole orquinoline.

In the context of the present invention, an aliphatic hydrocarbylradical or an alkyl group or an alkenyl or alkynyl group which maytypically contain 1 to 40 or else 1 to 20 carbon atoms and in whichindividual hydrogen atoms or CH₂ groups may also be replaced by theabovementioned groups are preferably understood to mean the methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl,n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl,heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl,butynyl, pentynyl, hexynyl, heptynyl or octynyl radicals. An alkoxygroup having 1 to 40 carbon atoms is preferably understood to meanmethoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy,n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy,cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 carbon atoms isunderstood to mean especially methylthio, ethylthio, n-propylthio,i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio,cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio,trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio,ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio,hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio,octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio,pentynylthio, hexynylthio, heptynylthio or octynylthio. In general,alkyl, alkenyl, alkynyl, alkoxy or thioalkyl groups according to thepresent invention may be straight-chain, branched or cyclic, where oneor more nonadjacent CH₂ groups may be replaced by the abovementionedgroups; in addition, it is also possible for one or more hydrogen atomsto be replaced by D, F, Cl, Br, I, CN or NO₂, preferably F, Cl or CN,further preferably F or CN, especially preferably CN.

An aromatic or heteroaromatic ring system which has 5-80 aromatic ringatoms and may also be substituted in each case by the abovementionedradicals and which may be joined to the aromatic or heteroaromaticsystem via any desired positions is especially understood to mean groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, cis- or trans-indenocarbazole, cis- ortrans-indolocarbazole, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, pyridine, quinoline, isoquinoline,acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine,quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene,1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole, or groups derivedfrom combinations of these systems. These groups may each be substitutedby the abovementioned radicals.

An aryloxy group as defined in the present invention is understood tomean an aryl group as defined above bonded via an oxygen atom. Ananalogous definition applies to heteroaryloxy groups.

An electron-deficient heteroaryl group in the context of the presentinvention is defined as a 5-membered heteroaryl group having at leasttwo heteroatoms, for example imidazole, oxazole, oxadiazole, etc., or asa 6-membered heteroaryl group having at least one heteroatom, forexample pyridine, pyrimidine, pyrazine, triazine, etc. It is alsopossible for further 6-membered aryl or 6-membered heteroaryl groups tobe fused onto these groups, as, for example, in benzimidazole orquinoline.

The wording that two or more radicals together may form a ring, in thecontext of the present description, shall be understood to mean, interalia, that the two radicals are joined to one another by a chemicalbond. This is illustrated by the following scheme:

In addition, however, the abovementioned wording shall also beunderstood to mean that, if one of the two radicals is hydrogen, thesecond radical binds to the position to which the hydrogen atom wasbonded, forming a ring. This shall be illustrated by the followingscheme:

In a further embodiment of the invention, not more than 1 X in formula(1) or in a quinazolinone base skeleton in formula (2) is N. Morepreferably, no X in formula (1) or formula (2) is N.

A preferred embodiment of the compound of the formula (1) is a compoundof the following formula (3), and a preferred embodiment of the compoundof the formula (2) is a compound of the following formula (4):

where the symbols and indices correspond to the definition of formulae(1) and (2).

In a preferred embodiment of the invention, the compound does notcomprise any aryl group or heteroaryl group having more than 22 aromaticring atoms.

In a preferred embodiment of the invention, the R¹, R² and R³ groups arethe same or different at each instance and, in the case of an aromaticor heteroaromatic ring system, are selected at each instance from thegroups having the following formulae (Ar-1) to (Ar-27):

-   where the symbols and indices correspond to the symbols and indices    of the formulae (1) and (2) and, in addition:-   Q is the same or different at each instance and is CR⁴ or N, where    not more than 3 Q symbols per cycle are N;-   E is the same or different at each instance and is (CR⁴)₂, NR⁴, O, S    or C═O;-   G at each instance is a single bond, (CR⁴)₂, NR⁴, O, S or C═O;-   n is 0 or 1, where n=0 means that no E group is bonded at this    position and R⁴ radicals are bonded to the corresponding carbon    atoms instead;-   Ar² is the same or different at each instance and is a bivalent    aromatic or heteroaromatic ring system which has 5 to 60 aromatic    ring atoms and may be substituted by one or more R⁴ radicals;-   Ar¹ are the same or different at each instance and are an aromatic    or heteroaromatic ring system which has 6 to 60 aromatic ring atoms    and may in each case also be substituted by one or more R⁴ radicals;    where the two Ar¹ may be joined and/or Ar¹ may be joined to Ar² via    at least one bridge K in each case;-   K is the same or different at each instance and is a single bond or    a divalent bridge selected from N(R⁴), B(R⁴), O, C═O, C(R⁴)₂,    Si(R⁴)₂ and S; and-   * represents the bond to the quinazolinone base skeleton,

In addition, the R² and R³ groups are selected from the groups of one ofthe following formulae (Ar1-1) to (Ar1-7):

-   where the symbols and indices correspond to the symbols and indices    of formula (1) and, in addition, for the formulae (Ar1-1) to    (Ar1-7):-   Q is the same or different at each instance and is CR⁴ or N, where    not more than 2 Q symbols per cycle are N;-   E is the same or different at each instance and is (CR⁴)₂, NR⁴, O, S    or C═O;-   G at each instance is a single bond, (CR⁴)₂, NR⁴, O, S or C=0;-   n is 0 or 1, where n=0 means that no E group is bonded at this    position and R⁴ radicals are bonded to the corresponding carbon    atoms instead;-   Ar¹ are the same or different at each instance and are an aromatic    or heteroaromatic ring system which has 6 to 60 aromatic ring atoms    and may in each case also be substituted by one or more R⁴ radicals;    where the two Ar¹ may be joined via at least one bridge K in each    case;-   K is the same or different at each instance and is a single bond or    a divalent bridge selected from N(R⁴), B(R⁴), 0, C═O, C(R⁴)₂,    Si(R⁴)₂ and S; and-   * represents the bond to the quinazolinone base skeleton.

In a further preferred embodiment, in the formula (Ar-1), 0, 1, 2 or 3 Qsymbols are N.

Preferred embodiments of the formula (Ar-15) are shown by the followingformulae (Ar-15-1) to (Ar-15-7):

where the symbols correspond to the symbols of the formula (Ar-15). Morepreferably, Q is always CR⁴.

In a further preferred embodiment, the R¹, R² and R³ groups are the sameor different at each instance and, in the case of an aromatic orheteroaromatic ring system, are selected from the groups having thestructures of the formulae (Ar-1) to (Ar-24), where the general formulaeare replaced by the respective particularly preferred embodiments of thefollowing formulae (Ar-1-1) to (Ar-21-1) (for example, formula (Ar-1) isreplaced by one of the formulae (Ar-1-1) to (Ar-1-9)):

where the symbols correspond to the symbols in formula (Ar-1) to(Ar-26). The formulae may be substituted by R⁴ at the unoccupiedpositions.

In a further embodiment of the invention, the R² and R³ groups areselected from the groups of one of the following formulae (Ar1-1) to(Ar¹-7), where the general formulae are replaced by the respectiveparticularly preferred embodiments of one of the following formulae(Ar1-1-1) to (Ar1-6-1) (for example formula (Ar1-1) is replaced by theformulae (Ar1-1-1)):

where the symbols correspond to the symbols in the formulae (Ar1-1) to(Ar1-5). The formulae may be substituted by R⁴ at the unoccupiedpositions.

In a further embodiment of the invention, the groups of formula (Ar-15)or preferred embodiments thereof are selected from the groups of one ofthe formulae (Ar-15-1-1a) to (Ar-15-7-6a):

where the symbols correspond to the symbols in formula (Ar-15). Theformulae may be substituted by R⁴ at the unoccupied positions.

In a further embodiment of the invention, the groups of formula(Ar-26-1) or preferred embodiments thereof are selected from the groupsof one of the formulae (Ar-26-1-1) to (Ar-26-1-6):

where the symbols correspond to the symbols in formula (Ar-26). Theformulae may be substituted by R⁴ at the unoccupied positions.

If present, L is the same or different at each instance and ispreferably a multivalent aromatic or heteroaromatic ring system having 6to 60 aromatic ring atoms. Preferred L groups comprise one or morestructures selected from the group comprising ortho-, meta- orpara-benzene, ortho-, meta- or para-biphenyl, terphenyl, especiallyortho-, meta- or para-terphenyl, quaterphenyl, especially ortho-, meta-or para-quaterphenyl, fluorene, 9,9′-spirobifluorene, furan, benzofuran,dibenzofuran, dibenzothiophene, pyrrole, indole or carbazole, orcombinations of these groups which may be joined to one another by oneor more single bonds and/or heteroatoms, preferably selected from N, Oand S. These groups may be substituted by one or more R⁴ radicals, butare preferably unsubstituted.

In a preferred embodiment, L comprises one or more structures selectedfrom the following formulae (Ar2-1) to (Ar2-15):

-   where the symbols and indices correspond to the symbols and indices    of formula (2) and, in addition:-   Q is the same or different at each instance and is CR⁴ or N, where    not more than 3 Q symbols per cycle are N;-   E is the same or different at each instance and is (CR⁴)₂, NR⁴, O, S    or C═O;-   G at each instance is a single bond, (CR⁴)₂, NR⁴, O, S or C=0;-   n is 0 or 1, where n=0 means that no E group is bonded at this    position and R⁴ radicals are bonded to the corresponding carbon    atoms instead;-   Ar² is the same or different at each instance and is a bivalent    aromatic or heteroaromatic ring system which has 5 to 40 aromatic    ring atoms and may be substituted by one or more R⁴ radicals;-   Ar¹ are the same or different at each instance and are an aromatic    or heteroaromatic ring system which has 6 to 60 aromatic ring atoms    and may in each case also be substituted by one or more R⁴ radicals;    where the two Ar¹ may be joined and/or Ar¹ may be joined to Ar² via    at least one bridge K in each case;-   K is the same or different at each instance and is a single bond or    a divalent bridge selected from N(R⁴), B(R⁴), 0, C═O, C(R⁴)₂,    Si(R⁴)₂ and S; and-   where, if two or more structures are present, the individual    structures are joined to one another by one or more single bonds,    NR⁴, 0 or S; and-   where L has, at n+m positions, a single bond to the quinazolinone    base skeleton according to the formula (2).

Preferably, this single bond to the quinazolinone base skeleton replacesa substitution by R⁴ at the respective position.

In a preferred embodiment, L comprises 1, 2, 3, 4, 5, 6, 7, 8 or 9structures selected from the formulae (Ar2-1) to (Ar2-15).

In a preferred embodiment, L comprises 1, 2 or 3 structures selectedfrom the formulae (Ar2-1) to (Ar2-10).

In a preferred embodiment of the invention, m+n is a value of 2 to 6,preferably of 2 to 5, more preferably of 2 to 4.

In a further embodiment of the invention, the formulae (Ar2-1) to(Ar2-15) are replaced by their preferred embodiments from the formulae(Ar2-1-1) to (Ar2-9-5):

where the symbols used correspond to the symbols for the formulae(Ar2-1) to (Ar2-15). The groups may be substituted by R⁴ at theunoccupied positions. They are preferably unsubstituted. The groupshave, at n+m positions, a single bond to the quinazolinone baseskeleton. At the same time, m+n must not exceed the number ofsubstitutable positions of L. For instance, the formula (Ar2-1-4) has upto three unoccupied positions.

In a further embodiment of the invention, the Ar² group in formula(Ar-22) comprises one or more of the structures of the formulae (Ar2-1)to (Ar2-15), preferably (Ar2-1) to (Ar2-14), or the preferredembodiments thereof, where the symbols and indices correspond to thesymbols and indices of the formulae (Ar2-1) to (Ar2-15), and, in thecase of two or more structures, these are joined to one another via oneor more single bonds or heteroatoms, such as O, NR⁴ or S. The structuresmay be substituted by R⁴ at unoccupied positions. Ar² is a divalentgroup. This means that it has a single bond to the quinazolinone baseskeleton and a bond to the N of the formula (Ar-22). The bond to the Nof the formula (Ar-22) is preferably a C—N single bond.

In a further embodiment of the invention, the Ar¹ groups in formula(Ar-22) are selected from one of the structures of the formula (Ar-1) to(Ar-25) or the preferred embodiments thereof, where the symbols andindices correspond to the symbols and indices of the formulae (Ar-1) to(Ar-25), and, in addition, * represents the bond to the N of the formula(Ar-22).

In a further embodiment of the invention, R¹ and R² are the same ordifferent at each instance and are a straight-chain alkyl, alkoxy orthioalkoxy group having 1 to 40 carbon atoms or a branched or cyclicalkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each ofwhich may be substituted by one or more R⁴ radicals, where one or morenonadjacent CH₂ groups may be replaced by C≡C, Si(R⁴)₂, Ge(R⁴)₂,Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴ and where oneor more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, oran aromatic or heteroaromatic ring system which has 5 to 60 aromaticring atoms, each of which may be substituted by one or more R⁴ radicals,or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ringatoms and may be substituted by one or more R⁴ radicals, or acombination of these systems; at the same time, two or more R¹substituents may also form a mono- or polycyclic, aliphatic or aromaticring system with one another;

In a preferred embodiment of the invention, R¹ and R² are the same ordifferent at each instance and are an aromatic or heteroaromatic ringsystem which has 5 to 60 aromatic ring atoms and may be substituted ineach case by one or more R⁴ radicals, or an aryloxy or heteroaryloxygroup which has 5 to 60 aromatic ring atoms and may be substituted byone or more R⁴ radicals, or a combination of these systems; at the sametime, two or more R¹ substituents together may also form a mono- orpolycyclic, aliphatic or aromatic ring system.

In a preferred embodiment of the invention, R¹ is the same or differentat each instance and is a structure selected from the formulae (Ar-1) to(Ar-27) or the preferred embodiments thereof and R² is the same ordifferent at each instance and is a structure selected from the formulae(Ar-1) to (Ar-27) and (Ar1-1) to (Ar1-7) or the respective preferredembodiments.

In a preferred embodiment of the invention, R³ is the same or differentat each instance and is selected from the group consisting of H, D, F,Si(R⁴)₃, CN, a straight-chain alkyl or alkoxy group having 1 to 10carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to10 carbon atoms, each of which may be substituted by one or more R³radicals, where one or more nonadjacent CH₂ groups may be replaced by Oand where one or more hydrogen atoms may be replaced by D or F, anaromatic or heteroaromatic ring system which has 6 to 60 aromatic ringatoms and may be substituted in each case by one or more R⁴ radicals,where two or more adjacent R³ substituents may optionally form a mono-or polycyclic aliphatic ring system which may be substituted by one ormore R⁴ radicals.

In a particularly preferred embodiment of the invention, R³ is the sameor different at each instance and is selected from the group consistingof H, D, F, a straight-chain alkyl group having 1 to 10 carbon atoms ora branched or cyclic alkyl group having 3 to 10 carbon atoms, each ofwhich may be substituted by one or more R⁴ radicals, an aromatic orheteroaromatic ring system which has 6 to 60 carbon atoms and may besubstituted in each case by one or more R⁴ radicals, where two or moreadjacent R³ substituents may optionally form a mono- or polycyclic,aliphatic ring system which may be substituted by one or more R⁴radicals.

In a preferred embodiment of the invention, R³ in the case of anaromatic or heteroaromatic ring system is a structure selected from theformulae (Ar-1) to (Ar-27) and (Ar1-1) to (Ar1-7) or the respectivepreferred embodiments.

In a preferred embodiment of the invention, R⁴ in the case of anaromatic or heteroaromatic ring system is a structure selected from theformulae (Ar-1) to (Ar-27) and (Ar1-1) to (Ar1-7) or the respectivepreferred embodiments, where, in addition:

-   Q is the same or different at each instance and is CR⁵ or N, where    not more than 3 Q symbols per cycle are N;-   E is the same or different at each instance and is (CR⁵)₂, NR⁵, O, S    or C═O;-   G at each instance is a single bond, (CR⁵)₂, NR⁵, O, S or C=0;-   n is 0 or 1, where n=0 means that no E group is bonded at this    position and R⁵ radicals are bonded to the corresponding carbon    atoms instead;-   Ar² is the same or different at each instance and is a divalent    aromatic or heteroaromatic ring system which has 5 to 60 aromatic    ring atoms and may be substituted by one or more R⁵ radicals;-   Ar¹ are the same or different at each instance and are an aromatic    or heteroaromatic ring system which has 6 to 60 aromatic ring atoms    and may in each case also be substituted by one or more R⁵ radicals;    where the two Ar¹ may be joined and/or Ar¹ may be joined to Ar² via    at least one bridge K in each case;-   K is the same or different at each instance and is a single bond or    a divalent bridge selected from N(R⁵), B(R⁵), O, C═O, C(R⁵)₂,    Si(R⁵)₂ and S; and-   * represents the bond to the substituted position.

In a further preferred embodiment, R⁴ which binds to a carbon bridge inan aromatic or heteroaromatic ring system, as, for example, in theformulae (Ar-12-1), (Ar-12-2), (Ar-12-3), (Ar-12-4), (Ar-13-1),(Ar-13-2), (Ar-13-3), (Ar-13-4), (Ar1-1-5-1), (Ar-15-3-1a) or (Ar2-9-2),is the same or different at each instance and is selected from the groupconsisting of a straight-chain alkyl group having 1 to 10 carbon atoms,a branched or cyclic alkyl group having 3 to 10 carbon atoms or anaromatic ring system having 6 to 30 carbon atoms which is as definedabove and which may be substituted by one or more R⁵ radicals. At thesame time, the two R⁴ groups may also form a ring system with oneanother, which may be aliphatic or, in addition to the definition of R⁴given above, may also be aromatic. Ring formation forms a Spiro system.

In a further preferred embodiment, R⁴ which binds to a nitrogen atom isselected from the group consisting of a straight-chain alkyl grouphaving 1 to 10 carbon atoms, a branched or cyclic alkyl group having 3to 10 carbon atoms or an aromatic ring system having 6 to 60 carbonatoms, especially an aromatic ring system having 6 to 60 carbon atomswhich is as defined above and which may be substituted by one or more R⁵radicals.

In a further preferred embodiment of the invention, the bonds from L tothe quinazolinone base skeletons are the same or different at eachinstance and are each selected from the group comprising a C—C, C—N orN—C bond.

Preferred combinations of the R¹ and R² radicals for the formulae (1)and (2) are given by the following table:

Compound R¹ R² 1-1 (Ar-1) (Ar-4) 1-2 (Ar-4) (Ar-1) 1-3 (Ar-12) (Ar-1)1-4 (Ar-1) (Ar-12) 1-5 (Ar-2) (Ar-12) 1-6 (Ar-12) (Ar-2) 1-7 (Ar-2)(Ar-1) 1-8 (Ar-1) (Ar-2) 1-9 (Ar-11) (Ar-1) 1-10 (Ar-1) (Ar-11) 1-11(Ar-1) (Ar-1) 1-12 (Ar-2) (Ar-2) 1-13 (Ar-12) (Ar-12) 1-14 (Ar-8) (Ar-1)1-15 (Ar-1) (Ar-8) 1-16 (Ar-1) (Ar-13) 1-17 (Ar-13) (Ar-1) 1-18 (Ar-23)(Ar-1) 1-19 (Ar-1) (Ar-23) 1-20 (Ar-23) (Ar-23) 1-21 (Ar-24) (Ar-24)1-22 (Ar-25) (Ar-25) 1-23 (Ar-23) (Ar-25) 1-24 (Ar-25) (Ar-23) 1-25(Ar-24) (Ar-25) 1-26 (Ar-25) (Ar-24) 1-27 (Ar-13) (Ar-13) 1-28 (Ar-1)(Ar-25) 1-29 (Ar-25) (Ar-1) 1-30 (Ar-24) (Ar-1) 1-31 (Ar-1) (Ar-24) 1-32(Ar-22) (Ar-1) 1-33 (Ar-1) (Ar-22)

For compounds of the formula (2), preference is given to the followingcombinations:

Compound L m n 2-1 (Ar2-2) 2 0 2-2 (Ar2-2) 0 2 2-3 (Ar2-2) 1 1 2-4(Ar2-9) 2 0 2-5 (Ar2-9) 0 2 2-6 (Ar2-9) 1 1 2-7 (Ar2-1) 0 3 2-8 (Ar2-1)3 0

The abovementioned embodiments may be combined with one another asdesired. More particularly, it is preferable to combine the preferredembodiments detailed above with one another.

Examples of preferred compounds of the above-detailed embodiments asusable with preference in organic electronic devices are the followingcompounds:

The compounds of the invention can be prepared by synthesis steps knownto those skilled in the art, for example bromination, Suzuki coupling,Ullmann coupling, Hartwig-Buchwald coupling, etc.

The preparation of the quinazolinone base skeleton proceeds, forexample, from 4H-3,1-benzoxazine-2,4(1H)-dione by reaction with an amineand an aldehyde, preferably with an aromatic amine and an aromaticaldehyde. This is followed by oxidation of the compound to give thequinazolinone base skeleton. This can be accomplished with standardoxidizing agents, such as iodine or potassium permanganate. In the caseof use of a group having more than one amino and/or aldehyde group,compounds of the formula (2) can be obtained.

When the compounds used have further suitable groups, compounds of oneof the formulae (1) and (2) can be formed by one or more couplingreactions, rearrangements and/or cyclizations.

The present invention therefore further provides a process for preparinga compound of formula (1) or formula (2), wherein the compound of theformula (1) or formula (2) is formed by one or more coupling reactions,rearrangements and/or cyclizations.

The synthesis methods shown above are of illustrative character and canbe modified in a suitable manner by the person skilled in the art in thefield of organic synthesis if this is advantageous for the synthesis ofparticular embodiments of compounds of the invention.

The above-described compounds of the invention, especially compoundssubstituted by reactive leaving groups, such as bromine, iodine,chlorine, boronic acid or boronic ester, may find use as monomers forproduction of corresponding oligomers, dendrimers or polymers. Suitablereactive leaving groups are, for example, bromine, iodine, chlorine,boronic acids, boronic esters, amines, alkenyl or alkynyl groups havinga terminal C—C double bond or C—C triple bond, oxiranes, oxetanes,groups which enter into a cycloaddition, for example a 1,3-dipolarcycloaddition, for example dienes or azides, carboxylic acidderivatives, alcohols and silanes.

The invention therefore further provides oligomers, polymers ordendrimers containing one or more compounds of formula (1) and/orformula (2), wherein the bond(s) to the polymer, oligomer or dendrimermay be localized at any unoccupied positions in formula (1) or formula(2). According to the linkage of the compound of the invention, thecompound is part of a side chain of the oligomer or polymer or part ofthe main chain.

An oligomer in the context of this invention is understood to mean acompound formed from at least three monomer units. A polymer in thecontext of the invention is understood to mean a compound formed from atleast ten monomer units.

The polymers, oligomers or dendrimers of the invention may beconjugated, partly conjugated or nonconjugated. The oligomers orpolymers of the invention may be linear, branched or dendritic.

In the structures having linear linkage, the units of formula (1) and/orformula (2) may be joined directly to one another, or they may be joinedto one another via a divalent group, for example via a substituted orunsubstituted alkylene group, via a heteroatom or via a divalentaromatic or heteroaromatic group.

In branched and dendritic structures, it is possible, for example, for3, 5 or more units of formula (1) and/or formula (2) to be joined via atrivalent or higher-valency group, for example via a trivalent orhigher-valency aromatic or heteroaromatic group, to give a branched ordendritic oligomer or polymer.

For the repeat units of formula (1) and/or formula (2) in oligomers,dendrimers and polymers, the same preferences apply as described abovefor the compounds of the invention.

For preparation of the oligomers or polymers, the monomers of theinvention are homopolymerized or copolymerized with further monomers.Suitable and preferred comonomers are chosen from fluorenes (for exampleaccording to EP 842208 or WO 2000/22026), spirobifluorenes (for exampleaccording to EP 707020, EP 894107 or WO 2006/061181), paraphenylenes(for example according to WO 1992/18552), carbazoles (for exampleaccording to WO 2004/070772 or WO 2004/113468), thiophenes (for exampleaccording to EP 1028136), dihydrophenanthrenes (for example according toWO 2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (forexample according to WO 2004/041901 or WO 2004/113412), ketones (forexample according to WO2005/040302), phenanthrenes (for exampleaccording to WO 2005/104264 or WO 2007/017066) or else a plurality ofthese units. The polymers, oligomers and dendrimers typically containstill further units, for example emitting (fluorescent orphosphorescent) units, for example vinyltriarylamines (for exampleaccording to WO 2007/068325) or phosphorescent metal complexes (forexample according to WO 2006/003000), and/or charge transport units,especially those based on triarylamines.

The polymers, oligomers and dendrimers of the invention haveadvantageous properties, especially high lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers of the invention are generally prepared bypolymerization of one or more monomer types, of which at least onemonomer leads to repeat units of the formula (1) and/or formula (2) inthe polymer. Suitable polymerization reactions are known to thoseskilled in the art and are described in the literature. Particularlysuitable and preferred polymerization reactions which lead to C—C andC—N bonds are as follows;

-   -   (A) SUZUKI polymerization    -   (B) YAMAMOTO polymerization    -   (C) STILLE polymerization and    -   (D) HARTWIG-BUCHWALD polymerization.

How the polymerization can be conducted by these methods and how thepolymers can then be separated from the reaction medium and purified isknown to those skilled in the art and is described in detail in theliterature, for example in WO 2003/048225, WO 2004/037887 and WO2004/037887.

The present invention thus also provides a process for preparing thepolymers, oligomers and dendrimers of the invention, which ischaracterized in that they are prepared by polymerization according toSUZUKI, polymerization according to YAMAMOTO, polymerization accordingto STILLE or polymerization according to HARTWIG-BUCHWALD. Thedendrimers of the invention can be prepared by processes known to thoseskilled in the art or in analogy thereto. Suitable processes aredescribed in the literature, for example in Frechet, Jean M. J.; Hawker,Craig J., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 2002/067343 A1 and WO 2005/026144 A1.

For the processing of the compounds of the invention from a liquidphase, for example by spin-coating or by printing methods, formulationsof the compounds of the invention are required. These formulations may,for example, be solutions, dispersions or emulsions. For this purpose,it may be preferable to use mixtures of two or more solvents. Suitableand preferred solvents are, for example, toluene, anisole, o-, m- orp-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF,methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially3-phenoxytoluene, (−)-fenchone, 1,2,3,5-tetramethylbenzene,1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole,2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole,3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol,benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene,dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycolbutyl methyl ether, diethylene glycol dibutyl ether, triethylene glycoldimethyl ether, diethylene glycol monobutyl ether, tripropylene glycoldimethyl ether, tetraethylene glycol dimethyl ether,2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene,octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of thesesolvents.

The invention therefore further provides a formulation, especially asolution, dispersion or emulsion, comprising at least one compound offormula (1) and/or formula (2) or at least one polymer, oligomer ordendrimer containing at least one unit of formula (1) and/or formula(2), and at least one phosphorescent dopant and at least one solvent,preferably an organic solvent. The way in which such solutions can beprepared is known to those skilled in the art and is described, forexample, in WO 2002/072714, WO 2003/019694 and the literature citedtherein.

The mixtures of the invention are suitable for use in an electronicdevice. An electronic device is understood to mean a device containingat least one layer containing at least one organic compound. Thecomponent may also comprise inorganic materials or else layers formedentirely from inorganic materials.

The present invention therefore further provides for the use of themixtures of the invention in an electronic device, especially in anorganic electroluminescent device.

The present invention still further provides an electronic devicecomprising at least one of the above-detailed mixtures of the invention.In this case, the preferences detailed above for the compound also applyto the electronic devices.

The electronic device is preferably selected from the group consistingof organic electroluminescent devices (OLEDs, PLEDs), organic integratedcircuits (0-ICs), organic field-effect transistors (0-FETs), organicthin-film transistors (0-TFTs), organic light-emitting transistors(0-LETs), organic solar cells (0-SCs), organic dye-sensitized solarcells, organic optical detectors, organic photoreceptors, organicfield-quench devices (0-FQDs), light-emitting electrochemical cells(LECs), organic laser diodes (0-lasers) and organic plasmon emittingdevices (D. M. Koller et al., Nature Photonics 2008, 1-4), preferablyfrom organic electroluminescent devices (OLEDs, PLEDs), especiallyphosphorescent OLEDs.

The organic electroluminescent device comprises cathode, anode and atleast one emitting layer. Apart from these layers, it may also comprisefurther layers, for example in each case one or more hole injectionlayers, hole transport layers, hole blocker layers, electron transportlayers, electron injection layers, exciton blocker layers, electronblocker layers and/or charge generation layers. It is likewise possiblefor interlayers having an exciton-blocking function, for example, to beintroduced between two emitting layers. However, it should be pointedout that not necessarily every one of these layers need be present. Inthis case, it is possible for the organic electroluminescent device tocontain an emitting layer, or for it to contain a plurality of emittinglayers. If a plurality of emission layers are present, these preferablyhave several emission maxima between 380 nm and 750 mm overall, suchthat the overall result is white emission; in other words, variousemitting compounds which may fluoresce or phosphoresce are used in theemitting layers. Especially preferred are systems having three emittinglayers, where the three layers show blue, green and orange or redemission (for the basic construction, see, for example, WO 2005/011013).These may be fluorescent or phosphorescent emission layers or elsehybrid systems in which fluorescent and phosphorescent emission layersare combined with one another.

The mixture of the invention according to the above-detailed embodimentsmay be used in different layers, according to the exact structure.Preference is given to an organic electroluminescent device comprising amixture of the invention or a compound of formula (1) and/or formula (2)or according to the preferred embodiments as matrix material forphosphorescent emitters. In this context, the above-detailed preferredembodiments also apply to the use of the materials in organic electronicdevices.

In a preferred embodiment of the invention, the compound of formula (1)and/or formula (2) or according to the preferred embodiments is used asmatrix material for a phosphorescent compound in an emitting layer. Inthis case, the organic electroluminescent device may contain an emittinglayer, or it may contain a plurality of emitting layers, where at leastone emitting layer contains at least one mixture of the invention or acompound of formula (1) and/or formula (2) as matrix material for aphosphorescent compound.

A further preferred embodiment of the present invention is the use ofthe compound of formula (1) or formula (2) or according to the preferredembodiments as matrix material for a phosphorescent emitter incombination with a further matrix material. Particularly suitable matrixmaterials which can be used in combination with the compounds of formula(1) or formula (2) or according to the preferred embodiments arearomatic ketones, aromatic phosphine oxides or aromatic sulphoxides orsulphones, for example according to WO 2004/013080, WO 2004/093207, WO2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives,e.g. CBP (N,N-biscarbazolylbiphenyl) or the carbazole derivativesdisclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527or WO 2008/086851, indolocarbazole derivatives, for example according toWO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, forexample according to WO 2010/136109 and WO 2011/000455, azacarbazolederivatives, for example according to EP 1617710, EP 1617711, EP1731584, JP 2005/347160, bipolar matrix materials, for example accordingto WO 2007/137725, silanes, for example according to WO 2005/111172,azaboroles or boronic esters, for example according to WO 2006/117052,triazine derivatives, for example according to WO 2010/015306, WO2007/063754 or WO 2008/056746, zinc complexes, for example according toEP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives,for example according to WO 2010/054729, diazaphosphole derivatives, forexample according to WO 2010/054730, bridged carbazole derivatives, forexample according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO2011/088877 or WO 2012/143080, triphenylene derivatives, for exampleaccording to WO 2012/048781, or lactams, for example according to WO2011/116865 or WO 2011/137951. It is likewise possible for a furtherphosphorescent emitter which emits at a shorter wavelength than theactual emitter to be present as co-host in the mixture.

The mixture of the compound of formula (1) or according to the preferredembodiments and the emitting compound contains between 99% and 1% byvolume, preferably between 98% and 10% by volume, more preferablybetween 97% and 60% by volume and especially between 95% and 80% byvolume of the compound of formula (1) or according to the preferredembodiments, based on the overall mixture of emitter and matrixmaterial. Correspondingly, the mixture contains between 1% and 99% byvolume, preferably between 2% and 90% by volume, more preferably between3% and 40% by volume and especially between 5% and 20% by volume of theemitter, based on the overall mixture of emitter and matrix material.

The term “phosphorescent dopant” (emitter) typically encompassescompounds where light is emitted via a spin-forbidden transition. Theseare compounds which, at room temperature, exhibit luminescence from anexcited state with spin multiplicity >1, for example via a transitionfrom an excited triplet state or a state with a higher spin quantumnumber, for example a quintet state. Suitable phosphorescent dopants areespecially compounds which, when suitably excited, emit light,preferably in the visible region, and also contain at least one atom ofatomic number greater than 20, preferably greater than 38, and less than84, more preferably greater than 56 and less than 80. Preference isgiven to using, as phosphorescent dopants, compounds containing copper,molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium,palladium, platinum, silver, gold and/or europium, especially compoundscontaining iridium, platinum or copper.

In the context of the present invention, all luminescent iridium,platinum or copper complexes are considered to be phosphorescentcompounds.

Particularly preferred phosphorescent dopants are compounds selectedfrom the formulae (D-1) to (D-6)

-   where R⁴ has the same definition as described above for formula (1),    and the further symbols used are as follows:-   DCy is the same or different at each instance and is a cyclic group    which contains at least one donor atom, preferably nitrogen, carbon    in the form of a carbene or phosphorus, or bears it as a substituent    via which the cyclic group is bonded to the metal, and which may in    turn bear one or more R⁴ substituents; the DCy and CCy groups are    joined to one another via a covalent bond;-   CCy is the same or different at each instance and is a cyclic group    which contains a carbon atom via which the cyclic group is bonded to    the metal, and which may in turn bear one or more R⁴ substituents;-   A is the same or different at each instance and is a monoanionic    ligand with bidentate chelation, preferably a diketonate ligand;-   B is the same or different at each instance and is a compound    comprising at least one donor atom, preferably nitrogen, carbon in    the form of a carbene or phosphorus, which binds to the metal.

At the same time, through formation of ring systems between two or moreR⁴ radicals, a bridge may also be present between the DCy and CCygroups. In addition, through formation of ring systems between two ormore R⁴ radicals, a bridge may also be present between two or threeCCy-DCy ligands or between one or two CCy-DCy ligands and the A ligand,or the two DCy-DCy ligands or DCy-DCy and DCy are present, such that thesystem is a polydentate or polypodal ligand system. This is especiallypreferred in the case of the Pt complexes of the formula (D-4), wherethe bridge between the two CCy-DCy ligands is preferably selected fromNR⁴ and C(R⁴)₂.

Preferably, B is a phosphanyl or arsanyl radical (P(R⁴)₂ or As(R⁴)₂).

Preference is given to compounds of one of the formulae (D-1) to (D-4).

The phosphorescent dopants may take the form of an individual compoundor may be bonded to polymers or oligomers.

Examples of phosphorescent dopants can be found in applications WO2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP1191612, EP 1191614, WO 2004/081017, WO 2005/033244, WO 2005/042550, WO2005/113563, WO 2006/008069, WO 2006/061182, WO 2006/081973, WO2009/146770, WO 2005/019373 and US 2005/0258742. Examples ofphosphorescent dopants comprising copper can be found in WO 2013/007707.In general, all phosphorescent complexes as used for phosphorescentOLEDs according to the prior art and as known to those skilled in theart in the field of organic electroluminescent devices are suitable foruse in the devices of the invention. It is also possible for the personskilled in the art, without exercising inventive skill, to use furtherphosphorescent complexes in combination with the compounds of theinvention in OLEDs.

Examples of suitable phosphorescent dopants are listed in the followingtable:

In a further embodiment of the invention, the organic electroluminescentdevice of the invention does not contain any separate hole injectionlayer and/or hole transport layer and/or hole blacker layer and/orelectron transport layer, meaning that the emitting layer directlyadjoins the hole injection layer or the anode, and/or the emitting layerdirectly adjoins the electron transport layer or the electron injectionlayer or the cathode, as described, for example, in WO 2005/053051. Itis additionally possible to use a metal complex identical or similar tothe metal complex in the emitting layer as hole transport or holeinjection material directly adjoining the emitting layer, as described,for example, in WO 2009/030981.

In the further layers of the organic electroluminescent device of theinvention, it is possible to use any materials as typically usedaccording to the prior art. The person skilled in the art is thereforeable, without exercising inventive skill, to use any materials known fororganic electroluminescent devices in combination with the inventivemixtures comprising the compounds of formula (1) or formula (2) oraccording to the preferred embodiments.

Additionally preferred is an organic electroluminescent device,characterized in that one or more layers are coated by a sublimationprocess. In this case, the materials are applied by vapour deposition invacuum sublimation systems at an initial pressure of less than 10⁻⁵mbar, preferably less than 10⁻⁶ mbar. It is also possible that theinitial pressure is even lower or higher, for example less than 10⁻⁷mbar.

Preference is likewise given to an organic electroluminescent device,characterized in that one or more layers are coated by the OVPD (organicvapour phase deposition) method or with the aid of a carrier gassublimation. In this case, the materials are applied at a pressurebetween 10⁻⁵ mbar and 1 bar. A special case of this method is the OVJP(organic vapour jet printing) method, in which the materials are applieddirectly by a nozzle and thus structured (for example M. S. Arnold etal., Appl. Phys. Lett. 2008, 92, 053301).

Preference is additionally given to an organic electroluminescentdevice, characterized in that one or more layers are produced fromsolution, for example by spin-coating, or by any printing method, forexample inkjet printing, LITI (light-induced thermal imaging, thermaltransfer printing), screen printing, flexographic printing, offsetprinting or nozzle printing. For this purpose, soluble compounds areneeded, which are obtained, for example, through suitable substitution.These methods are especially also suitable for oligomers, dendrimers andpolymers.

In addition, hybrid methods are possible, in which, for example, one ormore layers are applied from solution and one or more further layers areapplied by vapour deposition. For example, it is possible to apply theemitting layer from solution and to apply the electron transport layerby vapour deposition.

These methods are known in general terms to those skilled in the art andcan be applied by those skilled in the art without exercising inventiveskill to organic electroluminescent devices comprising the compounds ofthe invention.

The mixtures of the invention, when used in organic electroluminescentdevices, have one or more of the following surprising advantages overthe prior art:

-   1. Higher power efficiency of corresponding devices compared to    systems according to the prior art.-   2. Higher stability of corresponding devices compared to systems    according to the prior art, which is manifested particularly in a    much longer lifetime.-   3. The organic electroluminescent devices of the invention have a    reduced operating voltage.-   4. When the compounds of the invention are used as matrix material    for phosphorescent emitters, it is already possible to achieve very    good results with only a low emitter concentration in the region of    less than 10% by volume.-   5. The compounds of the invention have a very good thermal    stability.

The invention is now illustrated in detail by the examples which follow,without any intention of restricting it thereby.

WORKING EXAMPLES

Scheme 1 shows a synthesis of the base skeleton in analogy toMonatshefte fuer Chemie, 141(8), 877-881; 2010.

A second option for the synthesis is shown by Schemes 2a, 2b and 2c:

In this scheme, R is any radical and X is a leaving group, for example ahalide or tosylate.

First of all, a 4H-3,1-benzoxazine-2,4(1H)-dione is reacted with anamine and an aldehyde under acid catalysis. The corresponding2,3-dihydro-1H-quinazolin-4-one is obtained. The latter can be oxidizedwith potassium permanganate to the quinazolinone base skeleton. Becauseof the mild reaction conditions, it is possible to use substitutedaromatics. In this way, it is possible in a simple manner to introducegroups which allow further coupling reactions.

The leaving groups introduced can be converted, for example, byorganometallic coupling reactions. Scheme 2b cites, as an example, aBuchwald coupling or a Suzuki coupling.

By multiple coupling reactions, it is possible to form the compounds ofthe formula (2).

The formation of compounds of the formula (2) is also possible by themethod shown in Scheme 2c. This involves, in analogy to Scheme 2a,reacting a 4H-3,1-benzoxazine-2,4(1H)-dione derivative with an amine andan aldehyde under acid catalysis, where the amine and/or the aldehydehas at least one further amino and/or aldehyde group. Preference isgiven to amino or aldehyde groups bonded to aromatic or heteroaromaticring systems. In this way, two or more 4H-3,1-benzoxazine-2,4(1H)-dionederivatives are joined to one another. The compound obtained can beoxidized with potassium permanganate to the compound of formula (2).

Example 1: 2-(4-Bromophenyl)-3-phenyl-2,3-dihydro-1H-quinazolin-4-one

11 ml (121 mmol) of phenylamine and 18 g (110 mmol) of4H-3,1-benzoxazine-2,4(1H)-dione are refluxed in 500 ml of acetic acid.After 45 min, 22.4 g (121 mmol) of 4-bromobenzaldehyde dissolved inacetic acid are added and stirring of the mixture is continued underreflux overnight. After cooling, the solution is diluted with water/iceand filtered with suction. The residue is subjected to extraction bystirring with heptane and ethanol. The yield is 36 g (95 mmol), 86% oftheory.

In an analogous manner, it is possible to obtain the followingcompounds:

Ex. Reactant 1 Reactant 2 Reactant 3 Product [%] 1a

82 1b

86 1c

74 1d

70 1e

80 1f

68 1g

79 1h

84 1j

78 1i

81 1k

76 1l

76 1m

65 1n

70 1o

87

In analogy, the following compounds can be obtained when bifunctionalgroups are used:

Yield Ex. Reactant 1 Reactant 2 Reactant 3 Product [%] 1p

67 1q

61 1r

59 1s

48 1t

56

Example 2: 2-(4-Bromophenyl)-3-phenyl-3H-quinazolin-4-one

36 g (95 mmol) of2-(4-bromophenyl)-3-phenyl-2,3-dihydro-1H-quinazolin-4-one are dissolvedin 300 ml of DMF. 15 g (95 mmol) of potassium permanganate are added inportions to this solution, and the mixture is stirred at roomtemperature for 3 hours. After this time, the rest of the potassiumpermanganate is filtered off, and the solution is concentrated andpurified by chromatography (eluent: heptane/dichloromethane, 5:1). Theresidue is recrystallized from toluene and fromdichloromethane/isopropanol and finally sublimed under high vacuum;purity is 99.9%. The yield is 22 g (58 mmol), 61% of theory.

In an analogous manner, it is possible to obtain the followingcompounds:

Yield Ex. Reactant 3 Product [%] 2a

82 2b

86 2c

74 2d

70 2e

80 2f

68 2g

79 2h

84 2j

78 2l

81 2k

76 2l

82 2m

79 2n

81 2o

83

In analogy, the following compounds can be obtained when 2 eq. of KMnO₄are used:

Yield Ex. Reactant 1 Product [%] 2p

67 2q

61 2r

59 2s

48 2t

56

Example 3: 2-(4-Dibenzofuran-4-ylphenyl)-3-phenyl-3H-quinazolin-4-one

41.3 g (110.0 mmol) of 4-dibenzofuranboronic acid, 41 g (110.0 mmol) of2-(4-bromophenyl)-3-phenyl-3H-quinazolin-4-one and 44.6 g (210.0 mmol)of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml ofdioxane and 500 ml of water. Added to this suspension are 913 mg (3.0mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) ofpalladium(II) acetate, and the reaction mixture is heated under refluxfor 16 h. After cooling, the organic phase is removed, filtered throughsilica gel, washed three times with 200 ml of water and thenconcentrated to dryness. The residue is recrystallized from toluene andfrom dichloromethane/isopropanol and finally sublimed under high vacuum;purity is 99.9%. The yield is 41 g (90 mmol), corresponding to 82% oftheory.

In an analogous manner, the following compounds are obtained;

Yield Ex Reactant 1 Reactant 2 Product [%] 3a

83 3b

82 3c

81 3d

83 3e

88 3f

68 3g

75 3h

76 3j

83 3i

85 3k

88 3l

86 3m

76 3n

86 3o

67 3p

82

In analogy, the following compounds are obtained with 0.5 eq. of boroncompound:

Yield Ex. Reactant 1 Reactant 2 Product [%] 3q

86 3r

81 3s

83

Example 4:2-[4-(3,6-Diphenylcarbazol-9-yl)-phenyl]-3-phenyl-3H-quinazolin-4-one

32 g (102.4 mmol) of 3,6-diphenyl-9H-carbazole, 42 g (112 mmol) of2-(4-bromophenyl)-3-phenyl-3H-quinazolin-4-one and 2.3 g (10.2 mmol) of1,3-di[2-pyridyl]propane-1,3-dione, 28.3 g (204 mmol) of potassiumcarbonate and 1.9 g (10.2 mmol) of copper iodide in 1000 ml of DMF arestirred under reflux for 90 h. The solution is diluted with water andextracted twice with ethyl acetate, and the combined organic phases aredried over Na₂SO₄ and concentrated by rotary evaporation and purified bychromatography (EtOAc/hexane: 2/3). The residue is recrystallized fromtoluene and from dichloromethane and finally sublimed under high vacuum;purity is 99.9%. The yield is 47 g (77 mmol), corresponding to 69% oftheory.

In an analogous manner, the following compounds are obtained:

Yield Ex. Reactant 1 Reactant 2 Product [%] 4a

65 4b

66 4c

74 4d

71 4e

70 4f

65 4g

69 4h

72

Example 5: Production of the OLEDs

In examples 11 to 115 which follow (see Tables 1 and 2), the data ofvarious OLEDs are presented. Cleaned glass plaques (cleaning inlaboratory glass washer, Merck Extran detergent) coated with structuredITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozonefor 25 minutes (PR-100 UV ozone generator from UVP) and, within 20 min,for improved processing, coated with 20 nm of PEDOT:PSS(poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate), purchased asCLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland,spun on from aqueous solution) and then baked at 180° C. for 10 min.These coated glass plaques form the substrates to which the OLEDs areapplied.

The OLEDs basically have the following layer structure: substrate/holetransport layer (HTL)/interlayer (IL)/electron blocker layer (EBL)emission layer (EML)/optional hole blocker layer (HBL)/electrontransport layer (ETL) and finally a cathode. The cathode is formed by analuminium layer of thickness 100 nm. The exact structure of the OLEDscan be found in Table 1. A reference such as “4a” in the table relatesto the materials shown in the tables for the examples. The furthermaterials required for production of the OLEDs are shown in table 3.

All materials are applied by thermal vapour deposition in a vacuumchamber. In this case, the emission layer always consists of at leastone matrix material (host material) and an emitting dopant (emitter)which is added to the matrix material(s) in a particular proportion byvolume by co-evaporation. Details given in such a form as 4a:BIC1:TEG1(30%:60%:10%) mean here that the material 4a is present in the layer ina proportion by volume of 30%, BIC1 in a proportion of 60% and TEG1 in aproportion of 10%. Analogously, the electron transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterized in a standard manner. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in percent) as a function of luminance,calculated from current-voltage-luminance characteristics (IULcharacteristics) assuming Lambertian emission characteristics, and alsothe lifetime are determined. The electroluminescence spectra aredetermined at a luminance of 1000 cd/m², and the CIE 1931 x and y colourcoordinates are calculated therefrom. The parameter 01000 in Table 2refers to the voltage which is required for a luminance of 1000 cd/m².CE1000 and PE1000 respectively refer to the current and powerefficiencies which are achieved at 1000 cd/m². Finally, EQE1000 refersto the external quantum efficiency at an operating luminance of 1000cd/m².

The data for the various OLEDs are collated in Table 2.

TABLE 1 Structure of the OLEDs HTL IL EBL EML HBL ETL Ex. thicknessthickness thickness thickness thickness thickness I1 SpA1 HATCN SpMA12q:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (85%:15%) (50%:50%) 30 nm 30nm I2 SpA1 HATCN SpMA1 2r:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm(85%:15%) (50%:50%) 30 nm 30 nm I3 SpA1 HATCN SpMA1 2s:TEG1 IC1 10 nmST1:LiQ 70 nm 5 nm 90 nm (85%:15%) (50%:50%) 30 nm 30 nm I4 SpA1 HATCNSpMA1 2s:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30nm 30 nm I5 SpA1 HATCN SpMA1 2s:IC1:TEG1 ST1 ST1:LiQ 70 nm 5 nm 90 nm(42%:42%:16%) 10 nm (50%:50%) 30 nm 30 nm I6 SpA1 HATCN SpMA1 2f:TEG1IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm I7SpA1 HATCN SpMA1 4:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%)(50%:50%) 30 nm 30 nm I8 SpA1 HATCN SpMA1 3d:TER1 — ST1:LiQ 90 nm 5 nm130 nm (92%:8%) (50%:50%) 40 nm 40 nm I9 SpA1 HATCN SpMA1 3m:TEG1 IC1 10nm ST1:LiQ 70 nm 5 nm 90 nm (90%:15%) (50%:50%) 30 nm 30 nm I10 SpA1HATCN SpMA1 4a:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (90%:10%)(50%:50%) 30 nm 30 nm I11 SpA1 HATCN SpMA1 4a:IC1:TEG1 IC1 10 nm ST1:LiQ70 nm 5 nm 90 nm (45%:45%:10%) (50%:50%) 30 nm 30 nm I12 SpA1 HATCNSpMA1 4a:BIC1:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (30%:60%:10%)(50%:50%) 30 nm 30 nm I13 SpA1 HATCN SpMA1 4h:TEG1 IC1 10 nm ST1:LiQ 70nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 30 nm I14 SpA1 HATCN SpMA14h:BIC1:TEG1 IC1 10 nm ST1:LiQ 70 nm 5 nm 90 nm (60%:30%:10%) (50%:50%)30 nm 30 nm I15 SpA1 HATCN SpMA1 4h:TEG2 IC1 10 nm ST1:LiQ 70 nm 5 nm 90nm (90%:15%) (50%:50%) 30 nm 30 nm

TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at Ex. (V)(cd/A) (lm/W) 1000 1000 cd/m² E1 3.8 57 48 15.8% 0.32/0.63 E2 3.7 56 4715.7% 0.33/0.62 E3 3.7 59 50 16.5% 0.32/0.62 E4 3.9 61 50 16.6%0.32/0.63 E5 3.2 63 62 17.1% 0.33/0.63 E6 3.6 62 56 17.8% 0.32/0.62 E73.7 60 50 16.8% 0.32/0.63 E8 4.9 10.3 6.6 11.0% 0.67/0.33 E9 3.4 61 5717.4% 0.34/0.62 E10 3.6 49 43 13.7% 0.34/0.62 E11 3.1 52 54 14.7%0.33/0.62 E12 3.6 47 41 13.1% 0.32/0.63 E13 3.9 58 48 16.3% 0.32/0.63E14 3.9 54 43 15.1% 0.33/0.62 E15 3.8 57 47 16.1% 0.34/0.61

TABLE 3 Structural formulae of the materials for the OLEDs

HATCN

SpA1

LiQ

ST1

TEG1

TEG2

IC1

SpMA1

TER1

BIC1

IC1

2q

2r

2s

2f

3d

3m

4

4a

4h

1.-13. (canceled)
 14. A mixture comprising at least one phosphorescentdopant and at least one compound of one of the formulae (1) and (2):

where the symbols and indices used are as follows: X is the same ordifferent at each instance and is N or CR³, where not more than 2 X perheteroaryl group are N; L is the same or different at each instance andis an (m+n)-valent aromatic or heteroaromatic ring system which has 5 to60 aromatic ring atoms and is optionally substituted by one or more R⁴radicals; R¹ is the same or different at each instance and is H, D, F,Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂,Si(R⁴)₃, B(OR⁴)², OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkoxygroup having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxyor thioalkoxy group having 3 to 40 carbon atoms and is optionallysubstituted in each case by one or more R⁴ radicals, where one or morenonadjacent CH₂ groups is optionally replaced by C≡C, Si(R⁴)₂, Ge(R⁴)₂,Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴ and where oneor more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system which has 5 to 60aromatic ring atoms and is optionally substituted in each case by one ormore R⁴ radicals, or an aryloxy or heteroaryloxy group which has 5 to 60aromatic ring atoms and is optionally substituted by one or more R⁴radicals, or a combination of these systems; at the same time, two ormore R¹ substituents may also form a mono- or polycyclic, aliphatic oraromatic ring system with one another; R² is the same or different ateach instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂,S(═O)Ar, S(═O)₂Ar, CN, NO₂, Si(R⁴)₃, B(OR⁴)₂, OSO₂R⁴, N(Ar)₂, astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbonatoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3to 60 carbon atoms and is optionally substituted in each case by one ormore R⁴ radicals, where one or more nonadjacent CH₂ groups is optionallyreplaced by C≡C, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴),SO, SO₂, O, S or CONR⁴ and where one or more hydrogen atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system which has 5 to 60 aromatic ring atoms and isoptionally substituted in each case by one or more R⁴ radicals, or anaryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms andis optionally substituted by one or more R⁴ radicals, or a combinationof these systems; at the same time, two or more R² substituents may alsoform a mono- or polycyclic, aliphatic or aromatic ring system with oneanother; R³ is the same or different at each instance and is H, D, F,Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂,Si(R⁴)₃, B(OR⁴)₂, OSO₂R⁴, N(R⁴)₂, a straight-chain alkyl, alkoxy orthioalkoxy group having 1 to 40 carbon atoms or a branched or cyclicalkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and isoptionally substituted in each case by one or more R⁴ radicals, whereone or more nonadjacent CH₂ groups is optionally replaced by C≡C,Si(R¹)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S orCONR⁴ and where one or more hydrogen atoms is optionally replaced by D,F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemwhich has 5 to 60 aromatic ring atoms and is optionally substituted ineach case by one or more R⁴ radicals, or an aryloxy or heteroaryloxygroup which has 5 to 60 aromatic ring atoms and is optionallysubstituted by one or more R⁴ radicals, or a combination of thesesystems; at the same time, two or more adjacent R³ substituents may alsoform a mono- or polycyclic, aliphatic or aromatic ring system with oneanother; Ar is the same or different at each instance and is an aromaticor heteroaromatic ring system which has 6 to 60 aromatic ring atoms andmay also be substituted in each case by one or more R⁴ radicals, R⁴ isthe same or different at each instance and is H, D, F, Cl, Br, I, CHO,C(═O)R⁵, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, CN, NO₂, Si(R⁵)₃, B(OR⁵)₂,OSO₂R⁵, N(R⁵)₂, a straight-chain alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy orthioalkoxy group having 3 to 40 carbon atoms, each of which isoptionally substituted by one or more R⁵ radicals, where one or morenonadjacent CH₂ groups is optionally replaced by C≡C, Si(R⁵)₂, Ge(R⁵)₂,Sn(R⁵)₂, C═O, C═S, C═Se, P(═O)(R⁵), SO, SO₂, O, S or CONR⁵ and where oneor more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system which has 5 to 60aromatic ring atoms, each of which is optionally substituted by one ormore R⁵ radicals, or an aryloxy or heteroaryloxy group which has 5 to 60aromatic ring atoms and is optionally substituted by one or more R⁵radicals, or a combination of these systems; at the same time, two ormore adjacent R⁴ substituents may also form a mono- or polycyclic,aliphatic or aromatic ring system with one another; R⁵ is the same ordifferent at each instance and is H, D, F, Cl, Br, I, N(R⁶)₂, C(═O)R⁶,P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶, CR⁶═C(R⁶)₂, CN, NO₂, Si(R⁶)₃, B(OR⁶)₂,OSO₂R⁶, N(R⁶)₂, a straight-chain alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy orthioalkoxy group having 3 to 40 carbon atoms, each of which isoptionally substituted by one or more R⁶ radicals, where one or morenonadjacent CH₂ groups is optionally replaced by R⁶C═CR⁶, Si(R⁶)₂, C═O,C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, S or CONR⁶ and where one or morehydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN or NO₂, oran aromatic or heteroaromatic ring system which has 5 to 60 aromaticring atoms, each of which is optionally substituted by one or more R⁶radicals, or an aryloxy or heteroaryloxy group which has 5 to 60aromatic ring atoms and is optionally substituted by one or more R⁶radicals, or an aralkyl or heteroaralkyl group which has 5 to 60aromatic ring atoms and is optionally substituted by one or more R⁶radicals, or a combination of these systems; at the same time, two ormore adjacent R⁵ substituents together may also form a mono- orpolycyclic, aliphatic or aromatic ring system; R⁶ is the same ordifferent at each instance and is H, D, F or an aliphatic hydrocarbylradical having 1 to 20 carbon atoms or an aryl or heteroaryl group whichhas 5 to 60 ring atoms and is optionally substituted by one or more R⁷radicals, or a combination of these groups; R⁷ is the same or differentat each instance and is H, D, F or an aliphatic hydrocarbyl radicalhaving 1 to 20 carbon atoms; and m, n are the same or different at eachinstance and are 0, 1, 3, 4, 5, 6 or 7; where m+n is equal to orsuperior to
 2. 15. The mixture according to claim 14, wherein the atleast one compound of one of the formulae (1) and (2) is at least onecompound of one of the foiniulae (3) and (4):

where the symbols and indices have the definitions given in claim 14.16. The mixture according to claim 14, wherein the at least onephosphorescent dopant comprises a compound which, at room temperature,exhibits luminescence from an excited state with spin multiplicity >1.17. The mixture according to claim 16, wherein the at least onephosphorescent dopant comprises a compound which emits light undersuitable excitation and contains at least one atom of atomic numbergreater than
 20. 18. The mixture according to claim 17, wherein the atleast one phosphorescent dopant comprises a compound containing at leastone atom of atomic number greater than 56 and less than
 80. 19. Themixture according to claim 18, wherein the at least one phosphorescentdopant comprises a compound containing copper, molybdenum, tungsten,rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum,silver, gold and/or europium.
 20. The mixture according to claim 19,wherein the at least one phosphorescent dopant comprises a compoundselected from the formulae (D-1) to (D-4)

where R⁴ has the same definition as described above for formula (1), andthe further symbols used are as follows: DCy is the same or different ateach instance and is a cyclic group which contains at least one donoratom or bears it as a substituent via which the cyclic group is bondedto the metal, and which may in turn bear one or more R⁴ substituents;the DCy and CCy groups are joined to one another via a covalent bond;CCy is the same or different at each instance and is a cyclic groupwhich contains a carbon atom via which the cyclic group is bonded to themetal, and which may in turn bear one or more R⁴ substituents; A is thesame or different at each instance and is a monoanionic ligand withbidentate chelation, and B is the same or different at each instance andis a compound comprising at least one donor atom which binds to themetal.
 21. A process for producing a the mixture according to claim 14,wherein the compound of the formula (1) or formula (2) is formed by oneor more coupling reactions and/or cyclizations.
 22. A formulationcomprising at least one mixture according to claim 14 and one or moresolvents.
 23. A solution, a suspension or a miniemulsion comprising atleast one mixture according to claim 14 and one or more solvents.
 24. Anelectronic device comprising the mixture according to claim
 14. 25. Amatrix material for a phosphorescent compound which comprises a compoundaccording to either of the formulae (1) and (2)

where the symbols and indices used are as follows: X is the same ordifferent at each instance and is N or CR³, where not more than 2 X perheteroaryl group are N; L is the same or different at each instance andis an (m+n)-valent aromatic or heteroaromatic ring system which has 5 to60 aromatic ring atoms and is optionally substituted by one or more R⁴radicals; R¹ is the same or different at each instance and is H, D, F,Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂,Si(R⁴)₃, B(OR⁴)², OSO₂R⁴, a straight-chain alkyl, alkoxy or thioalkoxygroup having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxyor thioalkoxy group having 3 to 40 carbon atoms and is optionallysubstituted in each case by one or more R⁴ radicals, where one or morenonadjacent CH₂ groups is optionally replaced by C≡C, Si(R⁴)₂, Ge(R⁴)₂,Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴ and where oneor more hydrogen atoms is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system which has 5 to 60aromatic ring atoms and is optionally substituted in each case by one ormore R⁴ radicals, or an aryloxy or heteroaryloxy group which has 5 to 60aromatic ring atoms and is optionally substituted by one or more R⁴radicals, or a combination of these systems; at the same time, two ormore R¹ substituents may also form a mono- or polycyclic, aliphatic oraromatic ring system with one another; R² is the same or different ateach instance and is H, D, F, Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂,S(═O)Ar, S(═O)₂Ar, CN, NO₂, Si(R⁴)₃, B(OR⁴)₂, OSO₂R⁴, N(Ar)₂, astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbonatoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3to 60 carbon atoms and is optionally substituted in each case by one ormore R⁴ radicals, where one or more nonadjacent CH₂ groups is optionallyreplaced by Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO,SO₂, O, S or CONR⁴ and where one or more hydrogen atoms is optionallyreplaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromaticring system which has 5 to 60 aromatic ring atoms and is optionallysubstituted in each case by one or more R⁴ radicals, or an aryloxy orheteroaryloxy group which has 5 to 60 aromatic ring atoms and isoptionally substituted by one or more R⁴ radicals, or a combination ofthese systems; at the same time, two or more R² substituents may alsoform a mono- or polycyclic, aliphatic or aromatic ring system with oneanother; R³ is the same or different at each instance and is H, D, F,Cl, Br, I, CHO, C(═O)Ar, P(═O)(Ar)₂, S(═O)Ar, S(═O)₂Ar, CN, NO₂,Si(R⁴)₃, B(OR⁴)₂, OSO₂R⁴, N(R⁴)₂, a straight-chain alkyl, alkoxy orthioalkoxy group having 1 to 40 carbon atoms or a branched or cyclicalkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms and isoptionally substituted in each case by one or more R⁴ radicals, whereone or more nonadjacent CH₂ groups is optionally replaced by Si(R⁴)₂,Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, P(═O)(R⁴), SO, SO₂, O, S or CONR⁴ andwhere one or more hydrogen atoms is optionally replaced by D, F, Cl, Br,I, CN or NO₂, or an aromatic or heteroaromatic ring system which has 5to 60 aromatic ring atoms and is optionally substituted in each case byone or more R⁴ radicals, or an aryloxy or heteroaryloxy group which has5 to 60 aromatic ring atoms and is optionally substituted by one or moreR⁴ radicals, or a combination of these systems; at the same time, two ormore adjacent R³ substituents may also form a mono- or polycyclic,aliphatic or aromatic ring system with one another; Ar is the same ordifferent at each instance and is an aromatic or heteroaromatic ringsystem which has 6 to 60 aromatic ring atoms and may also be substitutedin each case by one or more R⁴ radicals, R⁴ is the same or different ateach instance and is H, D, F, Cl, Br, I, CHO, C(═O)R⁵, P(═O)(R⁵)₂,S(═O)R⁵, S(═O)₂R⁵, CN, NO₂, Si(R⁵)₃, B(OR⁵)₂, OSO₂R⁵, N(R⁵)₂, astraight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbonatoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3to 40 carbon atoms, each of which is optionally substituted by one ormore R⁵ radicals, where one or more nonadjacent CH₂ groups is optionallyreplaced by C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O, C═S, C═Se, P(═O)(R⁵),SO, SO₂, O, S or CONR⁵ and where one or more hydrogen atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system which has 5 to 60 aromatic ring atoms, eachof which is optionally substituted by one or more R⁵ radicals, or anaryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms andis optionally substituted by one or more R⁵ radicals, or a combinationof these systems; at the same time, two or more adjacent R⁴ substituentsmay also form a mono- or polycyclic, aliphatic or aromatic ring systemwith one another; R⁵ is the same or different at each instance and is H,D, F, Cl, Br, I, N(R⁶)₂, C(═O)R⁶, P(═O)(R⁶)₂, S(═O)R⁶, S(═O)₂R⁶,CR⁶═C(R⁶)₂, CN, NO₂, Si(R⁶)₃, B(OR⁶)₂, OSO₂R⁶, N(R⁶)₂, a straight-chainalkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or abranched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40carbon atoms, each of which is optionally substituted by one or more R⁶radicals, where one or more nonadjacent CH₂ groups is optionallyreplaced by R⁶C═CR⁶, Si(R⁶)₂, C═O, C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, Sor CONR⁶ and where one or more hydrogen atoms is optionally replaced byD, F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemwhich has 5 to 60 aromatic ring atoms, each of which is optionallysubstituted by one or more R⁶ radicals, or an aryloxy or heteroaryloxygroup which has 5 to 60 aromatic ring atoms and is optionallysubstituted by one or more R⁶ radicals, or an aralkyl or heteroaralkylgroup which has 5 to 60 aromatic ring atoms and is optionallysubstituted by one or more R⁶ radicals, or a combination of thesesystems; at the same time, two or more adjacent R⁵ substituents togethermay also form a mono- or polycyclic, aliphatic or aromatic ring system;R⁶ is the same or different at each instance and is H, D, F or analiphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aryl orheteroaryl group which has 5 to 60 ring atoms and is optionallysubstituted by one or more R⁷ radicals, or a combination of thesegroups; R⁷ is the same or different at each instance and is H, D, F oran aliphatic hydrocarbyl radical having 1 to 20 carbon atoms; and m, nare the same or different at each instance and are 0, 1, 2, 3, 4, 5, 6or 7; where m+n is equal to or superior to
 2. 26. The electronic deviceas claimed in claim 24, wherein the device is selected from the groupconsisting of organic electroluminescent devices, organic integratedcircuits, organic field-effect transistors, organic thin-filmtransistors, organic light-emitting transistors, organic solar cells,organic dye-sensitized solar cells, organic optical detectors, organicphotoreceptors, organic field-quench devices, light-emittingelectrochemical cells, organic laser diodes and organic plasmon emittingdevices.
 27. The electronic device according to claim 24, wherein thedevice is an organic electroluminescent device and the mixture is usedin an emitting layer.